Reexamination certificate



United States Patent 3,037,963 RESINOUS MATERIALS Ro'gerM.. Christensen,Richiand Township, Pa, assignor to Pittsburgh Plate Glass Company,Allegheny County,

Pa.,. a corporation of Pennsylvania.

No Drawing. Filed July -21,1958,-Ser.=-No;749,583r 15 Claims.(01.260-72) This. invention" relates. v.to novel resinous materials andmethods. for-the: preparation thereof, and pertains more. particularlyto aldehyde g-substituted amideinterpolymers;particularly-those whichare obtained-by react ing- -an-2-aldehyde with "an interpolymer,onecomponent of which is an unsaturated amide.

The recent commercialavailability, of-the versatile.

they have poor impact resistance, solvent resistance,-

chemical'resistance, and mar-resistance; Theuse-ofiormaldehydertointroduce methylol CH- OH) groups is one method-ofsecuring cross-linking and enhanced prop-r 35 containinginterpolymerstendwto be'unstable-on storage,

erties insuch interpolymers- However, such-,"methylol or :in:use-as'coating compositions-due .to the ease with which: such crosselinkingoccurs.

- It has now-- been-- discovered.- that-gext-rerne-ly useful-- resinousmaterials. can be-obtained-from aldehyde-substituted amide-interpolymersat least'SO percent, and preferably;90-percent to 100 percent of theamido'groups have .-a hydrogen atom replaced .-by groups of thestructure ROR wherein R is a lower aliphatic hydrocarbon radicalhaving-its connecting valences on: a single carbon atom, and R1. is-analkyl or .aralkyl-radical. The pres.-

ence'of the -ROR groups-intheinterpolymer chain-has a tremendous effectupon the-stability of the; polymer, and .makes it possible --to preparecoating-compositions,

and similar materials which possessvexcellentrshelf: 1ife'.-, Moreover,the polymers ofwthis type-.possess outstandingphysical-propertiesincluding toughness, mar. resistance and alkali resistance whenproperly-curedp Depending. upon: the "choice ,of monomers utilized-inpreparing the polymers, :1 wide .range of polymers, .fromsoft.flexiblematerials to very hard materials, can be readily obtained.

The exact mechanismwhereby theamide interpolymers are obtained is notdefinitely knowmbut is believed to.

begin by the formation initially of arelatively short chain solubleinterploymerhaving an approximate structure.

as follows, acrylamide being utilized for illustrative ,purposes:

High molecular weight interpoiymers containing 3,h37,%3 Patented June 5,1962 wherein M-representsa unit of-a monomeror monomers polymerizablewithv acrylamide, and n represents a whole number greater than. 1.

unit

H l? 45H)- The short chain,interpolymerdepicted structurally abovethen-reacts: with an aldehyde suchas. formaldehydeyin the presence of analkanol to give .thestructurez.

wherein M, n,.andR havethesignificance set-forth -h'ere-- inabove.

As indicated above; at leastgabout 50 percent of the R groups in the,interpolymer chain must be alkyl-or aralkyl I in order to obtain astable resinous composition. Those groups which are not alkylor aralkyl:will obviously be hydrogen atoms.

In'addition to preparing the resinous compositions. byv the methoddescribed .in the foregoing paragraph, that is,- byfirst,forminganinterpolymer of an unsaturated amide. such as acrylamide,and then,reacting the.interpolymera with an-.aldehyde.-such asformaldehydein the presence of an'alcohol, it-is alsopossible toprepare'these mate-- rials by first reacting the unsaturatedamideitwith'the.

aldehyde and ,fpolymerizing the .zresulting-materialwith other iethylenically' unsaturated monomers in the presence.;of: an alcohol. Forexample, acrylamidefland formaldehyde, can be reacted toform-methylolacryla'mide, which in turn can be polymerized with otherethylenic'allyunsaturated monomers and'either concurrently,or-subsequently be-reacted with an alcohol.

'Also, N-alkoxyalkyl acrylamides can be prepared by the"reaction'offacrylamide with1an alkanol solution of 5 an-aldehydeunder mildlyacidic conditions, and the resulting N-alkoxyalkyl acrylamidepolymerized with other ethylenically unsaturated 'monomers togive theresinous materials .of ,this invention. Regardless of the method bywhich .they are prepared, the useful. products of. this inventionareallcharacterized as being interpolymers of unsaturated amides in which atleast about 50 percent of the amido gr oups-have a-hydrogen-.-atom re-vplaced-.-by groups-ofthe structure ;-ROR wherein R and R have:themeanings set; .forthHhereinabove;

The; ethylenically unsaturatedfimonomeric. materials which .can 'bepolymerizedazwith unsaturated. amides to form useful: .interpolymers maybe: any 1 monomer con-- taining a-CH ':C group; preferably activated bya negative substituentz. Included among'the useful mono-- merspossessing the CH =C grouping are:-

For example, if styrene were utilized as the second monomer,.M wouldrepresentthe (1) Monoolefinic hydrocarbons, that is, monomers containingonly atoms of hydrogen and carbon, such as styrene, alpha-methylstyrene, alpha-ethyl styrene, alphabutyl styrene, and the like;

(2) Halogenated monoolefinic hydrocarbons, that is, monomers containingcarbon, hydrogen and one or more halogen atoms such asalpha-chlorostyrene, alpha bromostyrene, 2,5-dichlorostyrene,2,5-dibromostyrene, 3,4-dichlorostyrene, 3,4-difluorostyrene, ortho-,meta-, and parafluorostyrenes, 2,6-dichlorostyrene,2,6-difiuorostyrene,3- fluoro-4-chlorostyrene, 3-chloro-4 fluorostyrene,2,4,5-trichlorostyrene, dichloromonofluorostyr'enes, 2-chloropr0-pene-l, 2-chlorobutene-1,2-chlor0pentene-1, 2-chlorohexene-l,2-chloroheptene-l, 2-bromobutene l, Z-bromoheptene-1, Z-fluorohexene-l,2 fluorobutene l, 2-iodopropene-l, 2-iodopentene-l, 4-bromoheptene-1,4-chloroheptene-l, 4-fluoroheptene-1, cis andtrans-1,2-dichlorethylenes, 1,2-dibromoethylene, 1,2-difluoroethylene,1,2- diiodoethylene, chloroethylene (vinyl chloride),1,1-dichloroethylene (vinylidene chloride), bromoethylene,fiuoroethylene, iodoethylene, 1,l-dibromoethylene, 1,1-difluoroethylene, 1,1-diiodoethylene, 1,1,2,2-tetrafluoroethylene,1,l,2,2-tetrachloroethylene, l-chloro-2,2,2-trifluoroethylene, and thelike; I

(3) Esters of organic and inorganic acids such as vinyl acetate, vinylpropionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinylcaproate, vinyl en-anthate, vinyl benzoate, vinyl toluate, vinylp-chlorobenzoate, vinyl ochlorozenzoate, vinyl m-chlorobenzoate andsimilar vinyl halobenzoates, vinyl p-methoxybenzoate, vinylo-methoxybenzoate, vinyl p-ethoxybenzoate, methyl methacrylate, ethylmethacrylate, propyl methacrylate, butyl methacrylate, amylmethacrylate, hexyl methacrylate, heptyl methacrylate, octylmethacrylate, decyl methacrylate, methyl crontonate, ethyl crotonate andethyl tiglate;

Methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate,butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate,Z-ethylhexyl' acrylate, heptyl acrylate, octyl acryl-ate,3,5,5-trimethylhexylacrylate, decyl acrylate and dodecyl acrylate;

Isopropenyl acetate, isopropenyl propionate, isopro penyl butyrate,isopropenyl isobutyrate, isopropenyl valerate, isopropenyl caproate,isopropenyl enanthate, isopropenyl benzoate, isopropenylp-chlorobenzoate, isopropenyl o-chlorobenzoate, isopropenylo-bromobenzoate, isopropenyl m-chlorobenzoate, isopropenyl toluate,isopropenyl alphahhloroacetate and isopropenyl alpha-' bromopropionate;

Vinyl 'alpha-chloroacetate, vinyl alpha-'bromoacetate,

vinyl alpha-chloropropionate, vinyl alpha-bromopropio nate, vinylalpha-iodopropionate, vinyl alpha-chlorobutyrate, vinylalpha-chlorovalerate and vinyl alpha bromovalerate;

, Allyl chloride, allyl cyanide, allyl bromide, allyl fluoride, allyliodide, allyl chlorocarbonate, allyl nitrate, allyl-thiocyanate, allylformate, allyl acetate, allyl propionate, allyl butyrate, allylvalerate, allyl caproate, allyl 3,5 ,S-trimethylhexoate, allyl benzoate,allyl acrylate, allyl crotonate, allyl oleate, allyl chloroacetate,allyl trichloroacetate, allyl chloropropionate, allyl chlorovalerate,allyl lactate, allyl pymvate, allyl aminoacetate, allyl acetoacetate,allyl thioacetate, as well as methallyl esters corresponding to theabove allyl esters as well as esters from such alkenyl alcoholsbeta-ethyl allylnalcohol, beta propyl Dimethyl maleate, diethyl maleate,diallyl maleate,

dimethyl fumarate, diethyl fumarate, dimethallyl fumarate and diethylglutaconate;

(4) Organic nitriles such as acrylonitrile, methacrylonitrile,ethacrylonitrile, 3-octenenitrile, crotonitrile, oleonitrile, and thelike;

(5) Acid monomers such as acrylic acid, methacrylic acid, crotonic acid,S-butenoic acid, angelic acid, tiglic acid, and the like; i

(6) Monomeric dienes such as butadiene-l,3, Z-methyl positions of thisinvention, other unsaturated amidessuch as methacrylamide, itaconicdiamide, maleuric acid, and esters thereof as represented by the formulawherein R is an alkyl radical, and imide derivatives such as N-carbamylmaleimide of the structure may also be utilized.

It has been found that in those instances where a two componentinterpolymer prepared from an unsaturated polymerizable amide and asingle monomer polymer- .izable therewith is not completely suitable forfurther reaction with an aldehyde, useful modification of theinterpolymer can usually be obtained by including a third "with one ormore polymerizable monomers are most allyl alcohol, 1-butene-4-ol,2-methyl-butene-ol-4, 2(2,2- 5

dimethylpropyl)-l-butene-4-ol and l-pentene-4-ol;

Methyl alpha-chloroacrylate, methyl alpha-bromo acrylate, methylalpha-fluoroacrylate, methyl alpha-iodoacrylate, ethylalpha-chloroacrylate, propyl alpha-chlororeadily prepared 'by carryingout the polymerization in a solvent in which the unsaturatedpolymerizable amide, a white, crystalline solid, and the other monomer/sare soluble at reaction temperature, and under reflux temperatures.Butanol has proven to he a satisfactory solvent in most cases. Isopropylalcohol, butyl, Cellosolve, and mixtures of lbutauol or other loweralkauol with water can also be used advantageously as solvents. Somecare must be exercised when water is present in the sysacrylate,isopropyl alpha-bromoacrylate, amyl alpha chloroacrylate, octylalpha-chloroacrylate, 3,5,5-trimethylhexyl alpha-chloroacrylate, decylalpha-chloroacrylate,

methyl alpha-cyano acrylate, ethyl alpha-cyano acrylate,

amyl alpha-cyano acrylate decyl alpha-cyano;

acrylate;

tem as gummy precipitates may result, especially with the higher waterlevels. The presence of lower alcohols or water has been found tomoderate the speed of reaction by lowering the reflux temperature. Butylor ethyl 1 acetate, or other ester solvents, and hydrocarbons such asxylene or mixtures of solvents and the like may also be employed.Mixtures of alcohols and aromatic hydrocarbons are especially useful forthis purpose.

In carrying out the polymerization reaction a peroxygen type catalyst isordinarily utilized. Useful catalysts for this purpose include acetylbenzoyl peroxide, hydroxyheptyl peroxide, methyl ethyl ketone peroxide,cyclohexanone peroxide, cyclohexyl hydroperoxide, 2,4-dichlorobenzoylperoxide, cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide,methyl amyl ketone peroxide, acetyl peroxide, lauroyl peroxide, benzoylperoxide, methyl cyclohexyl hydroperoxide, p-chlorobenzoyl peroxide,di-t-butyl peroxide, peracetic acid, t-butyl permaleic acid, di-t-butyldiperphthalate, t-butyl perphthalic acid, t-butyl peracetate, and thelike. It has been found that two of the most economical of the aboveperoxygen compounds are entirely satisfactory in most instances; forexample, cumene hydroperoxide can be used advantageously at higherreflux temperatures, whereas benzoyl peroxide has been very efiective atlower reflux temperatures. For some polymerization reactions, mixturesof the above peroxygen compounds are used to secure desired conversions.The diazo compounds such as a phaalpha-azo-di-isobutyronitrile orp-methoxyphenyl diazothio-(2-naphthyl)ether, may also be used aspolymerization catalysts in the preparation of the unsaturatedpolymerizable amide interpolymers. Redox catalyst systems can also beemployed.

The quantity of catalyst employed can be varied considerably; however,in most instances it is desirable to utilize from about 0.1 percent to2.0 percent by weight of the monomeric components. If high viscositiesare desired, a low initial level of catalyst, followed by the necessaryadditions to get 100 percent conversion, is preferably employed. For lowviscosity interpolymers the bulk of the catalyst is added initially andlater additions used only to secure desired conversions. Larger amountsof catalyst added initially give lower viscosities.

Since it is desirable that the interpolymers of the unsaturatedpolymerizable amide with other ethylenically unsaturated monomers berelatively low in molecular Weight so that they can be dissolved at highsolids and low viscosities, a chain modifying agent or chain terminatoris ordinarily added to the polymerization mixture. The use of a loweralkanol such as butanol or a mixture of butanol and water as a solvent,together with high catalyst levels, helps considerably, but in mostinstances it is preferred to add controlled amounts of chain modifyingmaterials. The mercaptans, such as dodecyl mercaptan, tertiary dodecylmercaptan, octyl mercaptan, hexyl mercaptan, and the like areconventionally used for this purpose. However, other chain modifyingagents such as cyclopentadiene, allyl acetate, allyl carbamate,alpha-methyl styrene dimers, and alpha-methyl styrene itself can be usedto secure low molecular weights, as can unsaturated fatty acids oresters. carbons in the reaction mixture also are of assistance inmaintaining low molecular weight.

Another method for preparing the unsaturated polymerizable amideintenpolymers involves utilization of block or graft techniques.Conventional polymerization procedures ordinarily result in a randomdistribution of the components in the interpolymers. By block or graftmethods the components can be introduced into the composition in aregular sequence or order, each segment being of a certain length andperiodicity. These products can be made such that the unsaturatedpolymerizable amide portion is in a fixed position in the composition,this approach involving the preparation of segments with reactive endgroups or reactive sites along a preformed backbone from which or towhich other segments can be grown or attached. The properties ofmaterials prepared by this relatively new technique are known to bequite different in many instances from interpolymers in which thecomponents are randomly oriented. By the block or graft method, one canprepare, by choice, materials of difierent solubility, solvent and flameresistance, adhesion, water solubility, and, in fact, almost Aromatichydro- 7 any desired property can be tailored. into the interpolymer.

It is preferred that the aldehyde be reacted with an interpolymercontainingfrom about 5 percent to about 50 percent by weightof the unsaturated. polymerizable. amide, the balance being the otherethylenically' unsaturated monomer/ s. It has been found thatinterpolymers containing the higher levels of the unsaturatedpolymerizable amide or those monomers which ordinarily form hardhomopolymers, give hard and flexible films and'consequently can be usedas primary film formers, whereas interpolymers containing lower levelsor the unsaturated polymerizable amide with those monomerswhich.ordinarily form soft homopolymers tend to be softer and use: fulas plasticizers for nitrocellulose and similar materials. If more thanone ethylenically unsaturated monomer is polymerized with theunsaturated polymerizable amide, the proportions of such additionalmonomers utilized will depend upon the characteristics which suchmonomer or monomers will impart to the final interpolymer. For example,in some ternary interpolymer systems it may be desirable to utilizeabout 20 percent by Weight of the unsaturated polymerizable amide, and40 percent each of two additional monomers such as styrene andbutadiene, or in some instances, such as when acrylic acid is one of themonomers utilized, it is desirable that the interpolymer contain about20 percent of the unsaturated poly- 'merizable amide, about78 percent ofasecond ethylenically unsaturated monomer, and only about 2 percent ofacrylic acid. The amount of monomers necessary in anyinterpolymerization reaction can readily be determined by simpleexperiment.

The polymerization is best carried out by admixing the unsaturatedpolymerizable amide and the other monomer or monomers, the catalyst andchain modifying agent, if any, in the solvent, and refluxing theresulting solution for a time sufficient to obtain the desiredconversion. Ordinarily, the polymerization time will be from about 1hour to 16 hours. As indicated hereinabove, it may in some instances bedesirable to addonly a portion of the catalyst initially, the remainderbeing added in increments as the polymerization progresses. Externalcooling of the polymerization mixture or very accurate control of refluxconditions is important in carrying out the polymerization because ofthe very rapid reaction rate. Good agitation is also desirable.

Ordinarily, the monomers and solvent are charged in amounts which would.give a solids content of approximately 50 percent based on percentconversion to polymer. However, in the event that the unsaturatedpolymerizable amide is present in an amount of about 30 percent to 50percent by weight'of the total monomer charge, the monomers and solventshould be proportioned to give a solids content of about 30 percent orless in order to prevent the formation of a gel, especially uponreaction with formaldehyde. In such cases, a portion of the solvent canbe evaporated after polymer formation is complete in order to give anydesired solids content.

As indicated hereinabove, the interpolymers of an unsaturatedpolymerizable amide prepared according to-the method disclosed herein,are readily soluble in inexpensive organic solvents but aresubstantially water insoluble, this latter property being exceedinglyimportant in the preparation of coating compositions.

The useful resinous. materials of the present invention are obtained byreacting the interpolymers prepared-according to the methods describedabove with an aldehyde and either an alkanol or an aralkanol in suchamanner that at least about 50 percent of the amido groups have ahydrogen atom replaced by -ROR groups, wherein each R is an aliphatichydrocarbon radical, preferably, an alkylene radical, having itsconnecting valences on a single carbon atom, and R is an alkyl radicalor an aralkyl radical. Formaldehyde, in the form of an alcohol solutionthereof, or 2. formaldehyde yielding substance such 7 asparaformaldehydeor trioxymethylene, ispreferred. However, othermonoaldehydes, that is, aldehydes containing a single aldehyde (CHO)group, and preferably containing only atoms of carbon, hydrogen, andoxygen, including acetaldehyde, butyraldehyde, furfural, and the VEXAMPLES I TO VIII r These examples illustrate the preparation of theinterpolymers containing acrylamide. In each example butanolwas utilizedas asolvent and cumene hydroperoxide like, can'also be used. Aldehydescontaining two or more 5 as (fatalyst The polwfmnzatlon was carriedaldehyde groups, such as glyoxal, are unsatisfactory and admlxmg hmonomers m the butmfol and adding one should not be used inasmuch asthey cause gel formation half of the catalyst therem' The mlxture wasthen when reacted with amide interpolymers fluxed for two hours, and onehalf of the remaining cata- It is preferred that the alcohol utilized bebutanol. I y added- The Was again refluXed for two However, otheralkanols, including methanol, ethanol, hOl-IFS and the remainingcatalyst added- After an addipropanol, pentanol, hexanol, heptanol, andoctanol, as tional two hours of refluxing, substantially 100 percentwell as higher alkanols including those containing up to conversion tointerpolymer was obtained. The pertiabout 12 carbon atoms can also beemployed. Likewise, nent data are set forth in the following table:

7 Composition Preparation Properties Example Percent Percent PercentPercent Percent Percent reactive tertiary Percent Percent GardnerGardner- Water aerylaethyl styrene vinyl monomers dodecyl catalystsolids viscosity holdt solubility mide acrylate toluene in mercaptan'color butanol 15 85 47.5 1 2 45.8 Z2 7 4-5 0.124 25 75 30. 0 2 2 28.2 A-1-2 0. 152 15 85 47.5 1 2 46.5 Z3- 5 2-3 0.110 25 75 30.0 2. 4 25.9 A2-3 0.095 35 i 65 30.0 2 4 27.2 B- 2-3 0.187 45 40 50.0 1 2 48.5 U-W 5-60.220 40 50.0v 2 2 50.0 Z1 3-4 0.251 35 35 30 30. 0 2 4 2s. 5 A'- 4-5 0.37s

1 Based on reactive monomers present.

The solubility test was carried out by drying a sample of the resin to apowder and placing a weighed amount of this resin and a weighed amountof water into a bottle which was then rotated in a waterbath at 25 C.for 16 hours. The water was then filtered and a solids analysis carriedout to determine how much polymer had dissolved (grams per 100 grams ofsolution).

aralkanols such as benzyl alcohol can be utilized with good results.

It is ordinarily preferred to utilize two equivalents of formaldehydefor each amide group present in the interpolymer. However, this ratiomay be raised or lowered considerably if desired. For example, the ratiomay be as high as about 3.0 equivalents of formaledhyde for each amidegroup in the inteipolymer, or as low as about 0.3 equivalent offormaldehyde for each amide group in the interpolymer. Some of theformaldehyde utilized may be consumed in a side reaction producing adialkyl formal.

The reaction is preferably carried out in the presence of a mild acidcatalyst such as maleic anhydride. Other acid catalysts such as oxalicacid, hydrochloric acid, or sulfuric acid, may also be utilized withgood results. The quantity of catalyst employed may be varied Widely;hO'W- ever, in general, it is preferred to utilize from about 0.2percent to 1.0 percent by weight of catalyst, based upon the weight ofthe amide interpolymer which is reacted with the aldehyde.

The reaction of the amide interpolymer with the aldehyde can be carriedout simply by adding the aldehyde and catalyst (if one is utilized) tothe polymerization mixture obtained by polymerizing the amide and one ormore ethylenically unsaturated monomers, and refluxing the resultantmixture for a period of from about 3 to 5 hours or until a desiredviscosity or solids content is obtained. The water of condensation canbe removed by azeotropie distillation as may a portion of the solvent ifdesired. Preferably, the final resinous material will have a solidscontent of about 20 percent to 70 percent and a Gardner viscosity ofabout H to Z at 50 precent solids content. The following examplesillustrate in detail the preparation of resinous materials by thereaction of aldehydes wtih interpolymers of unsaturated polymerizableamides and ethylenically unsaturated monomers, and the use of theresulting resinous materials as film forming compositions; The examplesare not intended to limit the invention, however, for there are, ofcourse, numerous possible variations and modifications.

EXAMPLES IX TO XVII A series of resinous condensation products wasprepared by first polymerizing acrylamide with ethyl acrylate to form aninterpolymer, and subsequently condensing said interpolymer withformaldehyde. In preparing the ethyl acrylate-acrylamide interpolymer,the entire amount of catalyst was added at the start of thepolymerization reaction except in Example IX, wherein the catalyst wasadded in two increments, half of the catalyst being added initially andhalf mid-way during the polymerization reaction. In each run aconversion of substantially percent was obtained. The solvent for thefinal product was butanol in each instance.

The polymerization charge and polymerization procedure, inter-polymerproperties, the formaldehyde condensation procedure, the properties ofthe resinous condensation product and the films prepared therefrom areall set forth in the following table. In the table, the letters utilizedhave the following significance:

A-Benzoyl peroxide B-Butanol C-Cumene hydroperoxide D -Alpha-methylstyrene dimers E-Dodecyl mercaptan F- Isopro-panol G--Tertiary dodecylmercaptan Ill-H O. .I-Di-t-buty1 peroxide Example Example ExampleExample Example Example Example Example Example. 7 IX X ,1 XI- XII XIIIXIV XV XVI I XVIIi Polymerization charge and procedurez Acrylamide 125grams; 62.5 grams; 62.5 grams; 50 grams... 50 gramsr. 50grams-;'.250grams L 50-grams- 250 -gr amsz- Ethyl acrylat 375 grams; 187.5 grams.1875 grams; 150 grams. 150 grams. 150 grams. 750 grams;- ,150 grams..750gramsr- Catalyst 7.5 A 2.5 O 2.5 I 2 O grems 2 grams 2 0 grams" 0grams. 2 9 grams 10 0 grams.

grams. grams. grams.- I Modifier 2 Egrams 2 D grams. 6 D grams 10 Egrams. 4E-10H grams- 10E grams: Solvent: Butanol 600grams 250 grams" 250grams 200'grams 200 grams; 200 grams; 1,000grams'. 190'grams- 1,000grams.

125 grams f 6hours lhour lhour 2110urs 4hours 3hours 10 minutes. 4hours10,1'ninutes. Polymer properties:

Percent solids 46.8 49.6-; 40.9.; 52.2 V1scosity(Gardner).. 1 hour. 44minutes. 1 hour minutes. Very Very Very viscous." viscoush. j viscous:Formaldehyde condensation:

125 B Butanol $8 3 of 264 grams. grams. 132 grams 106 grams 106 grams.106 grams 530"grams 106 grams 530"grams.v

formaldchy de. 132 grams Maleic anhydride 3.6 grams 1.7 grams--. 1.7grams-" 1.4 grams-.- 1.4 grams 1.4 grams..- 7.0 grams. 1.4 grams 7.0grams. F Ilteflug ti11e;' 2hours; 'minutes 20'minutes. 1%hours.-- 1%hours. 15 minutes. 10 minutes 3 hours 10 minutes.

ma pro uc Percent solids 39.6 36.5 37.0 48.5 47.9 4818 43.8 50.2 43.8.Viscosity (Gardner) Z1 Z2 Z3-Z6 Z-ZI Z5 Z4 .22 U Z2Z3. Color (Gardner)4-5 1 1 1 1-2 1 1 1 1.'- Film properties: I

Sward hardness 2 26 20 2a 24 24- .22 2A 22. Impact resistance 43 43 4848 48 48 43 48.... Percent fiexibility 20 20 20 90 20 20 20 20 20.Alkali resistance. 1 32 ho'urs 2 hours 2 hours 2-16 hours 2 hours-.- 2%hours 2% hours..- 2% 11011184-. 48 hours..." 2% hours.

EXAMPLES XVIII TO XXIII In accordance with these examples, interpolymersof the acrylamide with'one or more of "the ethylenically unsaturatedmonomers disclosed hereinabove were prepared and condensed withformaldehyde to give useful resinous condensation products.

The polymerization in each example is carried out by admixing thepolymerizable components with a chain transfer "agent (if one wasutilized) in a solvent such as butanol or xylene, and adding thepolymerization :catalyst, either initially. or in increments throughoutthe poly;

merization reaction.- Thepolymerization mixture was EXAMPLE IXXXIV' Aninterpoly mer containing -15 percentacrylamide, 40 percent styrene andpercent ethyl acrylatewas prepared in butanol according tothemethod-'"of'Example VI. The-resulting interpolymer was then reacted withglyoxal in accordance with the .methOd utilized in Examples XVIII toXXIII. However, after only a few minutes of refluxing of theglyoxal-interpolymer'mixture; a

gel formed.

In addition to being useful film forming materials-the resinouscondensation products of the present invention are useful for many otherpurposes. For example, they 40 then refluxed bomb when butadlene-L3 havebeen found to; be compatible with many. other monom r) for a period O esu fi t. btal resinous materials including most alkydmesins, epoxyconvel'sloll 0f Substantlany J Percent-4 The PQ Y D resins :andepoxidized. oils, nitrocellulose, urea and .mellawn-charge, reflux Mme,lfltfifpolymer P p amine resins; and the like. The condensation productsaldehyde condensation procedure, and properties of the per se, or thecompositions obtained :by blending them resinous condensation productand films thereof are .rewith other of the materials described above,are in' turn ported in the following table: useful asmolding compoundsand as laminating materials.

Example XVIII ExampleXIX Example XX Example XXI Example XXII Example XXIII aerylamide... 20% acrylamide, 15% acrylamide, 20% acrylamide,v 20%acrylamide, (A) 25% methyl (A) 20% methyl (A) 25% styrene, ('A)40%styrene, (A) 40% styrene; 20%acry1arnide, methaerylate, methacrylate,(B) ethy1 (B):4091;buta.- (13) 40%:buta- :(A), %:vmyli.

(B) 60% ethyl (B) 60% ethyl acrylate diene diene toluene acrylateacrylate Polymerization charge and procedure:

Acrylamid 3 lbs- 40 grams 160 grams 250 grams. Monomer A 5 lbs 40 grams.1,000 grams. Monomer B 12-lbsgrams" Catalyst 90.8 0 grams... 2 A grams{38:3 g 3352: 16.0. I gramme.-. 25.0 A grams. Modifier 90.8 G grams 2 Dgrams 90.8 G grainsr..- 8.0 E'grams. 8.0 E gramsn.-. Solvent:

Butanol 20.0 lbs 200 grams 20.0 lhs 1,200 grams 1,200 grams 1,250 grams.Xylene 500'gramsi 500 gr-ams.-' Reflux Time .4 hours 1 hour 6 hours I 16hours (bomb)- 16hours (bomb) 10 hours. Polymer propertiesz- Percent-solids-- 52.5- 51.6.; 51.5. 25.1. 25.1 49.1. Viscosity (Gardner)- Z3"Z5-Z6' Z Z4Z5. Formaldehyde'eondensation:

Butanol solution of formaldehyde. 6.34 lbs 84.6 gr 6.34'lhs 339 grams339 grams 75/351 grams 1 resin. Maleic Anhydride; 36.3 gr 1.0 grams 36.3grams- 4.5 gr 4.5 grams 1.0 grams. Reflux Time 3 hours 3% hours- 3 hours4 hours 4 hour 16 hours. Final product:

Percent-snlirls-- 50.1.; 48.95:". 50.6.; 49.4.. 49.4.". 41.3. Viscosity(Gardner)- Y UV;. Z; Z- Z-Y. Color (Gardner); 3- 3-4. 3- 3-4 1-2. Filmproperties:

Sward hardness 20 22' a 28 34' 42. Impact resistan 9 48 96 48 1. Percentflexibility 20 20 20 20 20 2.6. Alkali resistance 3%. 24 hours 72 hours72hours- 72 hours.

Also, the amide interpolymer-aldehyde condensation V 7 products can bereacted with diisocyanates to form use ful materials.

invention cure readily at temperatures of about 300 F. and above withoutcatalyst to give hard, tough films. If

acrylamide, 25 percent styrene and 60 percent ethyl acrylate, theinterpolymer being condensed with formaldehyde, were" prepared and werelet down with repeat Films of theresinous condensation products of thiscatalysts such as phosphoric acid are used, cures as low at 200 F. forclear films, and 250 F. for pigmented films, can be used. The effect ofvarying temperatures, with and without a catalyst, upon the cure of theresinous condensation products is illustrated in the following tablewherein a condensation product of formaldehyde Impact Water Swardresistance resistance hardness (inch- (48 hours) pounds) 4 32Soft-White. 8 48 Soft. 16 48 Hard-Clear. 2 48 D0.

48 Do. 4 32 2 hours White-Soft. 0.5 percent phosphoric I 7 acid 200 1048 24 hours hard-Clear. 0.5 percent morpholine salt ofp-toluene-sultonic acid 200 10 l 38 2 hours whiteSoft. 0.5 percent poluenesullonic acid 200 12 48 24 hours a hard-Clear. None 250 8 44 2-24hours- Soft. 0.5 percent phosphoric acid 250 48 24 hours hard-Clear. 0.5percent morphohne salt of p-toluene-sulionic acid 250 22 48 Soit 24hours. 0.5 percent p-toluenesult'onic acid 250 22 38 24 hourshard-Clear.

300 26 48 D0. 0.5 percent morpholine salt of p-toluene-sulionic acid 30026 24 Do. 0.5 percent p-toluenesulfonic acid 300 22 26 Do.

Pigmented compositions in general require higher bakes than clear filmsto secure good cures. Grinds of titanium dioxide in a copolymercontaining -15 percent batches of-the same-composition to give threecompo-- sitions containing 40 percent solids in which the pigment level(based on solids) was 47 percent, 38 percent, 19 percent respectively.Draw downs on steel panels with a 0.003 inch draw bar were made whichdeposited' a film of about 1 mil thickness. The following tableillustrates that exceptionally good physical properties can be obtainedwith such highly pigmented films. G1oss was ex- -cellent in all casesand no yellowing occurred when the films were cured at 350 F.

H0, 30 minute Impact h pigment i cure Sward resistvel Catalysttemperahardness ance (percent) ture, F: (inchpounds) r r 47 None 350 2648 47 0.6 Jercent phosphoric 275 22 96 aei 38 None a .350 26 96 38 0.5piercent phosphoric 250 24 96 301 19 None 350 28 96 19 0.5 plercentphosphoric 250 2G 96 resins, an interpolymer containing percent ethylacrylate, 25,percent styrene, and 15 percent acrylamide was condensedwith formaldehyde. mer was then blended with epoxy resins of varyingmolecular weights, the interpolymer comprising percent by weight and theepoxy resins 25 percent by weight of ,the total resin solids. The bakingtemperatures and film properties are set forth below:

Epoxyresin 30 minute Impact Alkali V epoxide cure tem- Sward resistanceSolvent 7 Film appearance resistance equivalent perature, hardness(inch- (hours) 7 l... p u ds) 350 10 44 Butanol-methyl ethyl ke Clear l350 I 22 42 Methyl ethyl ketnne rin 40 350 28 Butanol-methyl ethyl ke100 400 44 48 7 Clear slightly yellow 100 1 350 26 48 Methyl ethylketone Clear 100 300 38 Butanol-cellosolve acetateoluene do 100 400 4630 Clear slightly yellow 100 300 46 96 Tol V ,7 Clear 7 V V, V r 100 30044 fiutanol-cellgsolve acetatedn 100 400 48 96 Clear slightly yellow 100370 1025 1309 36 96 Tol n Clear V, 100

p Plus'phosphoric'acid0.5 percent based on total resiii' solids.

The resulting poly- The resinous condensation-products of this inventioncan also be plasticized with various materials such as the epoxidizedoils, tricresyl. phosphate, blown castor oil, and the like. For example,a condensation product prepared by the reaction of formaldehyde with an80 percent from the class consisting of acrylamide, methacrylamide,

itaconic diamide, maleuric acid, alkyl'esters of maleuric.

acid and N-carbamyl maleimide, with atleast one other monomer containinga terminal CH C group, said interpolymer containing from aboutS percentto 50'per-- styrene-l5 percent acrylamide interpolymer was admixed 5cent of said amide, substantially all of the nitrogen atoms with varyingamounts of an epoxidized oil plasticizer in said interpolymer beingtrivalent nitrogen atoms, said (sold commercially as -Admex 710), andfilms of the interpolymer being characterized by havingat-leastaboubplasticized composition applied to metal sheets and baked. 50 percentof' the amido groupsthereof having a hydro- The pertinent data arerecorded below: gen 1 atom replaced by the structure Percent 30 minutelmpactresinous Percent cure Solution Film appearance Sward resist-F1ex1b11ity condenplastitemperar appearmee hardness ance percent 7 satecizer ture, F. I pounds) 90 10 300 Clear 54 75 25 300 do- 24 50 50 300-do Tacky 48 20 90 10 400 Sllghtly yello 5O 20 75 400 do 4a 48 20 50-50- 400 Dark yellow; 24- 48 20 90; 10 300 Clean, 44 20 75 25 1 300 5 -do42 48 20 50 50 300 (lo 48 20 1 Plu's phosphoric acid-(L6 percent basedontotalresinsolids;

In order to illustrate the importance of having; at v least about 5Opercent'of the amido groups with a hydro- A V EORrgen atom-replacedby,-ROR groups, wherein-R and R p p v 1 I have. meanings set forthvhereinabcve a Series of whereinR is'a memberof-tne class conslstlng of;hydrointerpolymers was prepared having the same proportions f' ly alldySaturated lower ph y l of styrene to ethyl acrylate toacrylamide asExample h l i 1S IPEmbBY 0f thedass conslsvtmg VI, except that thequantity of R alkyl groups in the alkyl radicals containing from about 1'to 12 carbon radical ROR Was intentionally varied from 0 percent atoms;and L radlcalsl" to 100 percent. Samples of these resins were thenstored A fil gat e Water insoluble Tesmous at temperatures of F. and F.both in the compos1t1on"compr1s1ng an Intel-polymer of 'monomerspresence and absence of a phosphoric acid catalyst, and conslstmgFssfsntlauy of m f ethyl acryla-tle observed periodically to determinethe stability thereof.- 10 Styrene, Sald llltefpolymel coff'lalmng P Thestability data are recorded in the following table: fm afirylamldebsubslantlauy an of the nitrogen atoms 1n=sa1d mterpolymer beingtrivalent nitro- Percent genatoms, said interpolymer being characterizedby hav- Sample Percent phos: Temperingat least about 5.0 percent'of theamidogroups thereof number egg? &9g; 1%? Gelanon having a hydrogen atomsreplaced by the-structurealyst CH' OR wherein R is lower 'alkyl. 0 78 Ng 1 5 v k l 1 0 140' o i We S 3.A thermosettmg, ungelled, Waterinsoluble 'resmous 1 g gg composition comprising an interpolymer'ofmonomers 0 78 Do: 50 consisting essentially of .acrylamide, ethyl.acryl'ate and 1 2 vinyl toluene, said interpolymer containing from.about 0 140 Do. 5 percent to SO percent "ofacrylamide;substantially all"8 1% 38: of the nitrogen atoms is said interpolymer being trivalent 1 78D nitrogen atoms, "said interpolymer' being characterized by' g B8;having at least about 'SOpercent' of the amido groups 1 78 Do. thereofhaving-a hydrogenatoms replaced by the struc- 0 140 Qdays. w 1 7s lday 1140 Shours CI-I OR 0 78 Qdays iggg \Vh%l-1-l'l- R -1S-lOW6l alkyL- 1 140Gened'befm heating 4. A thermosetting,ungelled, waterinsoluble resinousV composition comprising .an 'interpolymer ofmonomers g i f giv set ie tr the i g consisting essentially of acrylarnide and vinyl toluene, ta 6i ga g q t said interpolymer containing from about=5 percent toSO- fi io f a 3 E b 9 T Y fl percent of acrylamide, substantiallyall of thenitrogen 3; i Sum 3; ts are i tamedw atoms in said interpolymer beingtrivalent nitrogen atoms," 0 er 2 an; sdslc fit e l Proparlo or Pentanosaid-interpolymer beingcharacterized by havingsat -least flii s ipplizatio ii is Z cciiri iiiiiation in part of copendirig about 50 percentof the amido groups thereof having a t t r f' hdro en atom e la db h tapphcation, Serial No. 584,473, filed May 14, 1956, 1 r p Ce y t etincture which in turn is a continuation-in-part of abandoned-ap- 2 iplication, Serial No. 490,409, filed February 24, 71955. wherein R islower alkyL' I claim: 5. A'thermosetting, ungelled, water insolubleresinous. L'Athermosettmg, ungelled, water insoluble resinouscomposition comprising-an interpolymeriof monomers compositioncomprising an interpolymer of monomersconsistingessentiallyoffacrylamide, ethyl yacrylate and consistingessentially of an unsaturated amide selected methyl methacrylate, said'interpolymer containing fromabout percent to 50 percent of acrylamide,substantiallyall of the nitrogen atoms in said interpolymer beingtrivalent nitrogen atoms, said interpolymer being characterized byhaving at least about 50 percent of the amido groups thereof having ahydrogen atom replaced by the structure ---CH2OR1 wherein R is loweralkyl.

6. A thermosetting, ungelled, water insoluble resinous compositioncomprising an interpolymer of monomers consisting essentially ofacrylamide, styrene and butadiene 1,3, said interpolymer containing fromabout 5 percentto 50 percent of acrylamide, substantially all of thenitrogen atoms in said interpolymer being trivalent nitrogen atoms, saidinterpolymer being characterized by having at least about 50 percent ofthe amide groups thereof having a hydrogen atom replaced by thestructure CH OR stantially water insoluble interpolymer of monomersconsisting essentially of an unsaturated amide selected from the classconsisting of acrylamide, methacrylarnide, itaconic diamide, maleun'cacid, alkyl esters of maleuric acid, and N-carbamyl maleimide,'with atleast one other monomer containing a terminal CH =C group, saidinterpolymer containing from about 5 percent to 50-percent of saidamide, substantially all of the nitrogen atoms in said interpolymerbeing trivalent nitrogen atoms, said refluxing of said interpolymer andformaldehyde being carried out in admixture with a member of the classconsisting of an alkanol containing from about 1 to 12 carbon atoms, andbenzyl alcohol, and an acid catalyst selected from the class consistingof carboxylic acids and mineral acids, there being present in theadmixture from 0.2 equivalent to 3.0 equivalents of formaldehyde foreach amide group in said interpolymer, the resinous condensation productresulting from said refluxing step being characterized by having atleast about 50 percent of the amide groups thereof having a hydrogenatom replaced by the structure CH OR whereinR is a member of the classconsisting of alkyl radicals containing from about 1 to 12 carbon atoms,and benzyl radicals.

8. The method of'preparing a thermosetting, ungelled, water insoluble,film-forming resinous condensation product which comprises refluxingformaldehyde with a substantially water insoluble interpolymer ofmonomers consisting essentially of acrylamide, ethyl acrylate andstyrene, said interpolymer containing from about 5 percent to 50 percentof acrylamide, substantially all of the nitrogen atoms in saidinterpolymer being trivalent nitrogen atoms, said refluxing of saidinterpolymer and formaldehyde being carried out in admixture with loweralkanol and an acid catalyst selected from the class consisting ofcarboxylic acids and mineral acids, there being present in the admixturefrom 0.2 equivalent to 3.0 equivalents of formaldehyde for each amidegroup in said interpolymer, the resinous condensation product resultingfrom said refluxing step being characterized by having at least about 50percent of the amido groups thereof haying ahydrogen atom replaced bythe structure -CH OR wherein R is lower alkyl.

9. The method of preparing a thermosetting, ungelled,v

having at least about 50 percent of the amido groups thereof having ahydrogen atom replaced by the structure wherein R is lower alkyl.

10. The method of preparing a thermosetting, ungelled, water insoluble,film-forming resinous condensation product which comprises refluxingformaldehyde with "a substantially water insoluble interpolymer ofmonomer consisting essentially of acrylamide and vinyl toluene,'saidinterpolymer containing from aboutS percent -to 50 percent ofacrylamide, substantially all of the nitrogen atoms in said interpolymerbeing trivalent nitrogen atoms, said refluxing of said interpolymer andformaldehyde being carried out in admixture with lower alk-anol and anacid catalyst selected from the class consisting of carboxylic acids andmineral acids, there being present in the admixture from 0.2 equivalentto 3.0 equivalents of formaldehyde for each amide group in saidinterplo-ymer, the resinous condensation product resulting from saidrefluxing step being characterized by having at least about 50 percentof the arnido groups thereof having a hydrgoen atom replaced by thestructure wherein R is lower alkyl.

11. The method of preparing a thermosetting, ungelled, water insoluble,film-forming resinous condensati on product which comprises refluxingformaldehyde with a substantially water insoluble interpolymer ofmonomers consisting essentially of acrylamide, ethyl acrylate and methylmethacrylate, said interpolymer containing from about 5 percent to 50percent of acrylamide, substantia-lly all of the nitrogen atoms in saidinterpolymer being trivalent nitrogen atoms, said refluxing of said,

interpolymer and formaldehyde being carried out in admixture with loweralkanol and an acid catalyst selected from the class consisting ofcarboxylic acids and mineral acids, there being present in the admixturefrom 0.2 equivalent to 3.0 equivalents of formaldehyde for each amidegroup in said interpolymer, the resinous condensation product resultingfrom said refluxing step being characterized by having at least about 50percent of the amido groups thereof having a hydrogen atom replaced bythe structure CH OR wherein R is lower alkyl.

12. The method of preparing a thermosetting, ungelled, water insoluble,film-forming resinous condensation product which comprises refluxingformaldehyde with er alkanol and an acid catalyst selected from theclass,

consisting of carboxylic acids and mineral acids, there being present inthe admixture from 0.2 equivalent to 3.0 equivalents of formaldehyde foreach amide group in said interpolymer, the resinous condensation productresulting from said refluxing step being characterized by having atleast about 50 percent of the amido groups thereof having a hydrogenatom replaced by the structure CH OR wherein R is lower alkyl.

13. A thermosetting, ungelled, water insoluble resinous compositioncomprising an interpolymer of monomers consisting essentially ofacrylamide, a lower alkyl acrylate, and styrene, said interpolymercontaining from about percent to 50 percent of acrylamide, substantiallyall of the nitrogen atoms in said interpolymer being trivalent nitrogenatoms, said interpolymer being further characterized by having at leastabout 50 percent of the amido groups thereof having a hydrogen atomreplaced by the structure -CH OR wherein R is lower alkyl.

14. The method of preparing a thermosetting, ungelled, water insoluble,film-forming resinous condensation product which comprises refluxingformaldehyde with a substantially water insoluble interpolymer ofmonomers consisting essentially of acrylamide, a lower alkyl acrylate,and styrene, said interpolymer containing from about 5 percent to 50percent of acrylamide, substantially all of the nitrogen atoms in saidinterpolymer being trivalent nitrogen atoms, said refluxing of saidinterpolymer and formaldehyde being carried out in admixture with alower alkanol and an acid catalyst selected from the class consisitingof carboxylic acids and mineral acids, there being present in theadmixture from 0.2 equivalent to 3.0 equivalents of formaldehyde foreach amide group in said interpolymer, the resinous condensation productresulting from said refluxing step being characterized :by having atleast about percent of the amido groups thereof having a hydrogen atomreplaced by the structure CH OR wherein R is lower alkyl.

15. An article having a metallic surface having as a coating thereon ahardened film of the resinous composition of claim 1. 1

References Cited in the file of this patent UNITED STATES PATENTS2,173,005 Strain Sept. 12, 1939 2,808,383 Fikentscher et a1. Oct. 1,1957 2,810,713 Melamed Oct. 22, 1957 2,839,514 Shokal et al June 17,1948 FOREIGN PATENTS 467,492 Great Britain June 11, 1937 United StatesPatent 19 Christenson A 45 Certificate Issued Apr. 16, 1985 54 RESINOUSMATERIALS [75] Inventor: Roger M. Christenson, Richland Township,Allegheny County, Pa.

[73] Assignee: Pittsburgh Plate Glass Company,

Allegheny County, Pa.

Reexamination Request:

No. 90/000,468, Nov. 14, 1983 Reexamination Certificate for:

Patent No.: 3,037,963 Issued: Jun. 5, 1962 Appl. No.: 749,583 Filed:Jul. 21, 1958 Related US. Application Data [63] Continuation-impart ofSer. No. 584,473, May 14, 1956, which is a continuation-in-part of Ser.No. 490,409, Feb. 24, 1955, abandoned.

[51] Int. c1. C08F 8/28; C08L 61/20 [52] US. Cl. 525/154; 525/156;

525/385; 525/386; 526/301; 526/304; 526/306 [58] Field of Search260/80.5, 86.1, 88.1,

[56] References Cited U.S. PATENT D OCUMENTS 2,870,116 1/1959 Vogel eta1. 260/45.5 2,870,117 l/1959 Vogel et al. 260/455 2,978,437 4/1961Christenson 260/72 Primary Examiner-Theodore Pertilla EXEMPLARY CLAIM 1.A thermosetting, ungelled, water insoluble resinous compositioncomprising an interpolymer of monomers consisting essentially of anunsaturated amide selected from the class consisting of acrylamide,methacrylamide, itaconic diamide, maleuric acid, alkyl esters ofmaleuric acid and N-carbamyl maleimide, with at least one other monomercontaining a terminal CH :C group, said interpolymer containing fromabout 5 percent to 50 percent of said amide, substantially all of thenitrogen atoms in said interpolymer being trivalent nitrogen atoms, saidinterpolymer being characterized by having at least about 50 percent ofthe amido groups thereof having a hydrogen atom replaced by thestructure wherein R is a member of the class consisting of hydrogen,furyl, and a saturated lower aliphatic hydrocarbon radical, and R is amember of the class consisting of alkyl radicals containing from about 1to 12 carbon atoms, and benzyl radicals.

REEXAMINATION CERTIFICATE AS A RESULT OF REEXAMINATION, IT HAS ISSUEDUNDER 35 U.S.C. 307 BEEN DETERMINED THAT= The patentability of claims1-15 is confirmed. NO AMENDMENTS HAVE BEEN MADE TO THE PATENT

